CN115769384A - Method for treating waste solar cell - Google Patents
Method for treating waste solar cell Download PDFInfo
- Publication number
- CN115769384A CN115769384A CN202180045297.1A CN202180045297A CN115769384A CN 115769384 A CN115769384 A CN 115769384A CN 202180045297 A CN202180045297 A CN 202180045297A CN 115769384 A CN115769384 A CN 115769384A
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- China
- Prior art keywords
- solar cell
- cell module
- furnace
- ceramic support
- thermal decomposition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/20—Waste processing or separation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/82—Recycling of waste of electrical or electronic equipment [WEEE]
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- Environmental & Geological Engineering (AREA)
- Thermal Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
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- Microelectronics & Electronic Packaging (AREA)
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Abstract
A method for continuously treating waste solar cells according to the present invention is a method for continuously treating waste solar cells, including a heating step of: heating a solar cell module having a resin back sheet or the like in a thermal decomposition furnace to melt and oxidatively decompose a resin component contained in the solar cell module; the heating step is performed as follows: moving the solar cell module from an inlet to an outlet of a pyrolysis furnace in a state where the solar cell module is placed on a porous ceramic support (a) and the ceramic support (a) is placed on a porous material (B) supporting a transition metal oxide; the thermal decomposition furnace includes a temperature raising section at which the temperature of the solar cell module rises and a combustion section at which the resin component is oxidatively decomposed, and the oxygen concentration in the combustion section is controlled to be in a range of 6vol% or more and less than 15 vol%.
Description
Technical Field
The present invention relates to a method for treating a waste solar cell. More specifically, the present invention relates to a method for recovering valuable substances by removing resin components such as a back sheet and a sealing resin layer from a solar cell module and separating the components into glass, a cell, silver, an aluminum frame, and the like.
Background
To realize a low-carbon society, acceleration of reduction of CO by using renewable energy represented by solar power generation is being advanced 2 . Although the introduction of solar power generation has made remarkable progress, on the other hand, a technical problem of recycling at the time of discarding of a solar cell module has been pointed out.
The conventional solar cell module has a structure of three layers, namely a surface layer made of toughened glass, an inner side layer made of a sealing resin layer and a back plate. In the sealing resin layer, wires (interconnectors) for connecting the battery cells of the solar battery to each other are wired. The sealing resin is required to have transparency, flexibility, adhesiveness, tensile strength, weather resistance, and the like, and an ethylene-vinyl acetate copolymer (hereinafter, abbreviated as "EVA") is generally used and functions to adhere a tempered glass, a battery cell, and a back sheet by heating and pressurizing. When this solar cell module is heated in an oxidizing atmosphere by an electric furnace or the like, EVA melts at 80 to 120 ℃, a reaction of removing acetic acid of EVA occurs at around 350 ℃, and a thermal decomposition reaction of polyethylene portion as a main chain rapidly proceeds at around 450 ℃. A technique of performing such thermal decomposition to recover and utilize a solar cell module is disclosed (see patent documents 1 and 2).
However, since the thermal decomposition reaction proceeds explosively at around 450 ℃, thermal decomposition of a solar cell module having a size of about 1m × 2m causes a fire, and is not suitable for a large scale. In order to solve the above problems, a method for recovering a constituent material of a solar cell element is disclosed, which comprises the steps of: in a continuous heat treatment furnace in which the oxygen concentration fed into the furnace is maintained at 1.0 vol% or more and 3.0 vol% or less, acetic acid gas, which is one of EVA decomposition gases, is released and removed in a preheating decomposition part set at 300 to 400 ℃, and then EVA decomposition gases other than acetic acid are desorbed in a heat treatment part set at 400 to 550 ℃, and the EVA sealing material is removed from the solar cell element, thereby separating the cell part and the glass substrate (see patent document 3).
Further, the present applicant has proposed a method for recovering a valuable substance from a solar cell module having a resin back sheet and a sealing resin layer, the method comprising: a stacking step of stacking the solar cell module on a heat-resistant porous molded body so that the back surface is positioned on the lower side; and a heating step of heating the stack including the solar cell module and the porous molded body in a heating furnace in an oxidizing atmosphere having an oxygen concentration of 15% or more, melting a resin component, and then burning the resin component (see patent document 4).
Documents of the prior art
Patent document
Non-patent document
Non-patent document 1, high-molecular corpus, vol.64.No.9 (2007)
Disclosure of Invention
Problems to be solved by the invention
In the method provided in patent document 3, the oxygen concentration is controlled to be very low so as not to cause a rapid combustion reaction, and the resin component such as EVA is thermally decomposed under heating conditions of 2 stages. However, controlling the oxygen concentration and temperature in the furnace under the conditions of patent document 3 is complicated, and is not a simple method because of the extremely high skill in operation.
Further, most of the materials of the back sheets of the solar cells of the early applications of patent documents 1 to 3 are polyvinyl fluoride (hereinafter, abbreviated as "PVF") having weather resistance, and at present, polyethylene terephthalate (hereinafter, abbreviated as "PET") which is cheaper is the mainstream, and back sheets of two or three layers of PVF/PET, PVDF/PET, PVF/PET/PVF, PVDF/PET/PVDF, and the like laminated with a fluorine-based resin such as PET single layer, PVF, or polyvinylidene fluoride (hereinafter, abbreviated as "PVDF") are often used, and back sheets using PET are in the majority.
Although conventional thermal decomposition methods have no problem because fluorine-based resins such as PVF and PVDF are thermally decomposed at the same temperature as EVA, PET melts at 250 ℃, starts thermal decomposition at around 400 ℃, and has benzene rings and ester groups, thus involving a variety of thermal decomposition reactions. There are cases where carbides having benzene rings bonded to each other in a complicated manner are produced as by-products to form "soot" as a black paint, and the glass having "soot" adhered thereto is difficult to reuse. In addition, it has also been reported that 9% of the residue of the "soot" remains even when burned at 850 ℃ (see non-patent document 1).
Therefore, in the technique of patent document 3 in which the oxygen concentration is reduced, PET is not completely thermally decomposed even if EVA is thermally decomposed, and therefore, if a solar cell module using a back sheet to which PET is added is subjected to a heat treatment, the "soot" is simply generated and inorganic powder such as titanium oxide and calcium carbonate contained in the back sheet remains, and thus a more advanced separation technique is required to recover and utilize valuable substances.
On the other hand, in the method of patent document 4, by disposing a heat-resistant material supporting a transition metal oxide in a furnace, it is possible to suppress "soot" generated when an aromatic resin such as PET is burned, and it is possible to easily recover and dispose valuable substances reusable in a solar cell module. However, when a solar cell module is subjected to continuous heat treatment in an oxidizing atmosphere having an oxygen concentration of 15% or more, the temperature control is greatly biased to the upper limit by a rapid increase in temperature due to explosive combustion with flame, and stable treatment is difficult.
In view of the above, an object of the present invention is to provide a method for continuously treating waste solar cells by stable temperature control in order to recycle valuable substances contained in a solar cell module having a back sheet made of resin or the like.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above-mentioned problems. As a result, the inventors have found that a resin component can be gently and stably burned and removed by continuously performing a heat treatment in a furnace while moving a solar cell module from an inlet to an outlet of the thermal decomposition furnace in a state where the solar cell module is placed on a porous ceramic support and the ceramic support is placed on a porous material supporting a transition metal oxide, and controlling the oxygen concentration in a combustion part at a stage where the resin component is oxidatively decomposed to a specific range, and as a result, the treatment can be performed with stable temperature control, and have completed the present invention.
That is, the present invention relates to a method for continuously treating waste solar cells, which comprises: a solar cell module having a resin back sheet and a sealing resin layer is heated in a pyrolysis furnace to melt and oxidize and decompose a resin component contained in the solar cell module, wherein the heating step is performed by: the solar cell module is moved in a furnace from an inlet to an outlet of the thermal decomposition furnace in a state where the solar cell module is placed on a porous ceramic support (A) and the ceramic support (A) is placed on a porous material (B) supporting a transition metal oxide, and the thermal decomposition furnace includes a temperature raising section at a stage where the temperature of the solar cell module rises and a combustion section at a stage where the resin component is oxidatively decomposed, and the oxygen concentration of the combustion section is controlled to be in a range of 6vol% or more and less than 15 vol%.
ADVANTAGEOUS EFFECTS OF INVENTION
In the present invention, the resin component such as EVA and PET melted before ignition penetrates into the heat-resistant porous molded article, and the surface area is enlarged, and the combustion progresses gently, so that a rapid combustion reaction does not occur, and the combustion can be stably performed. Further, the "soot" generated when an aromatic resin such as PET is burned can be suppressed, and valuable substances that can be reused in a solar cell module can be easily recovered.
Drawings
Fig. 1 is a schematic view (with an aluminum frame) showing one embodiment of the present invention.
Fig. 2 is a schematic view (without an aluminum frame) showing one embodiment of the present invention.
Fig. 3 is a schematic view showing an overview of the thermal decomposition furnace used in the examples and comparative examples.
Fig. 4 is a graph showing changes in the furnace temperature and the oxygen concentration in examples and comparative examples.
Detailed Description
The present invention will be described in detail below.
The method for treating waste solar cells according to the present invention is a method for continuously treating waste solar cells, including a heating step of: a solar cell module having a resin back sheet and a sealing resin layer is heated in a thermal decomposition furnace to melt and oxidatively decompose a resin component contained in the solar cell module,
the heating step is performed as follows: moving the solar cell module in the furnace from the inlet to the outlet of the pyrolysis furnace in a state where the solar cell module is placed on a porous ceramic support (A) and the ceramic support (A) is placed on a porous material (B) supporting a transition metal oxide,
the thermal decomposition furnace includes a temperature raising section at which the temperature of the solar cell module rises and a combustion section at which the resin component is oxidatively decomposed, and the oxygen concentration in the combustion section is controlled to be in a range of 6vol% or more and less than 15 vol%.
< heating Process >
The heating step in the treatment method of the present invention is as follows: the resin component contained in the solar cell module is melted and oxidatively decomposed by heating the solar cell module having the resin back sheet and the sealing resin layer in the thermal decomposition furnace.
In the heating step, the solar cell module is moved from the inlet to the outlet of the pyrolysis furnace in the furnace in a state where the solar cell module is placed on the porous ceramic support (a) and the ceramic support (a) is placed on the porous material (B) supporting the transition metal oxide (see fig. 1). In this case, the solar cell module is preferably placed on the ceramic support (a) so that the back sheet surface is positioned on the lower side. In order to improve the processing efficiency of the waste solar cells, it is preferable to continuously move a plurality of solar cell modules in a heated state in the thermal decomposition furnace. When the object to be treated including the solar cell module, the ceramic support (a) and the porous material (B) is subjected to heat treatment, the object may be placed in a tray made of iron with a lattice or the like in order to prevent collapse or fall of the object while the object is moving in the furnace.
In the heating step, the thermal decomposition furnace includes a temperature raising section at which the temperature of the solar cell module rises and a combustion section at which the resin component is oxidatively decomposed (burned). In general, the inlet side of the thermal decomposition furnace is a temperature increasing portion and the outlet side is a combustion portion, but it is not necessary to define the boundary between the temperature increasing portion and the combustion portion in the thermal decomposition furnace as long as the resin component is melted and oxidatively decomposed as the temperature of the solar cell module increases as it moves from the inlet side to the outlet side in the furnace.
The combustion in the present invention means: an oxidation reaction in which organic substances such as EVA and PET contained in a back sheet, a sealing resin layer, and the like constituting a solar cell module react with oxygen in the atmosphere.
Therefore, the combustion temperature may be appropriately determined depending on the resin constituting the back sheet, but is preferably 425 to 575 ℃. If the temperature is 425 ℃ or higher, the temperature is higher than the thermal decomposition temperature of EVA and PET, and combustion occurs. Further, when the temperature is 575 ℃ or lower, rapid combustion can be suppressed, and glass breakage of the solar cell module can be prevented.
The melting starts to occur at a temperature lower than the combustion temperature. In order to obtain the combustion temperature, the temperature of the solar cell module is generally gradually increased from room temperature before entering the thermal decomposition furnace, and the melting temperature can be obtained in the course of the temperature increase.
The heating in the heating step should be performed in the thermal decomposition furnace in consideration of the treatment of the exhaust gas and the like. The thermal decomposition furnace is not particularly limited as long as it is a thermal decomposition furnace such as a gas furnace or an electric furnace capable of obtaining the combustion temperature and charging the object to be treated including the porous material (B), the ceramic support (a), and the solar cell module, and a known thermal decomposition furnace can be used.
The method for heating the inside of the thermal decomposition furnace is not particularly limited as long as the combustion temperature can be obtained. For example, in the case of a gas furnace, a method of heating an oxygen-containing gas with a gas nozzle or the like and circulating the gas in a thermal decomposition furnace is exemplified. Examples of the oxygen-containing gas include a mixed gas of a combustible gas such as liquefied petroleum gas or city gas and air.
In the heating step, the oxygen concentration in the combustion part is controlled to be in a range of 6vol% or more and less than 15vol%, whereby the resin component can be removed by burning gently and stably. The lower limit of the oxygen concentration is preferably 7vol%, more preferably 8vol%, and the upper limit is preferably 14.8vol%, more preferably 14.5vol%. Even if the oxygen concentration instantaneously deviates from the above range, there is no particular problem in operation as long as the oxygen concentration can be immediately controlled within the above range.
The method of controlling the oxygen concentration in the combustion portion is not particularly limited, and for example, in the case of a gas furnace using a mixed gas of liquefied petroleum gas and air as an oxygen-containing gas, the mixing ratio of air can be adjusted according to the oxygen concentration in the combustion portion.
In the method of the present invention, it is preferable that valuable substances remaining on the ceramic support (a) are recovered after the heating step. The valuable substance is preferably at least 1 selected from the group consisting of glass, a cell, silver, and an aluminum frame. The silver is derived from, for example, an electrode.
In the method of the present invention, in order to efficiently recover the valuable substances, it is also effective to provide a metal mesh or the like between the solar cell module and the ceramic support (a) before the heat treatment, which does not prevent the resin melted during combustion from moving to the ceramic support (a), and to recover the valuable substances after the treatment together with the metal mesh. This is because the processed product after melting and burning of the resin as the seal tape becomes a state in which glass, battery cells, and the like are dispersed on the ceramic support body, and is difficult to recover.
< solar cell Module >
The solar cell module usable in the present invention can be used as long as it is a solar cell module having a resin back sheet of a non-double-sided glass type. Specifically, a single crystal silicon solar cell, a polycrystalline silicon solar cell, an amorphous silicon solar cell, a heterojunction solar cell, a CIS solar cell, a CIGS solar cell, a CdTe solar cell, and the like can be cited. The aluminum frame of the solar cell module can be removed before thermal decomposition from the advantage that the ceramic support (a) does not need to be cut according to the size of the aluminum frame, and therefore the operation is easy, or can be removed after thermal decomposition in order to reduce the possibility of glass breakage at the time of removal.
< ceramic support (A) >)
The porous ceramic support (a) usable in the present invention may be used without any limitation as long as it is stable at a combustion temperature (specifically, about 425 to 575 ℃) described later and has a porous structure. Specific examples of the material include stable and conventional ceramic materials such as alumina, zirconia, silicon nitride, silicon carbide, cordierite, ferrite, barium titanate, lead zirconate titanate, forsterite, zircon, mullite, steatite, and aluminum nitride.
The pore diameter of the porous material is not particularly limited, but is preferably about 0.1 to 5mm which is easily penetrated when EVA, PET or the like is melted at about 450 ℃. The number of pores on the surface is also not particularly limited, and is desirably 5 to 50 pixels per inch (ppi). The porosity is not limited at all, and is desirably about 50 to 95%. Particularly, a material having a three-dimensional skeleton structure with continuous pores is preferably used.
The shape of the ceramic support (a) is not particularly limited, but a plate-shaped ceramic support is preferably used so that the resin used in the solar cell does not fall. In addition, from the viewpoint of suppressing the generation of "soot" due to the leakage of the molten resin component to the outside of the ceramic support body (a), the size (area) of the surface of the ceramic support body (a) on which the back sheet is stacked is preferably as large as possible within a range in which the back sheet can be fitted into the aluminum frame without removing the aluminum frame (see fig. 1), and is preferably larger than the bottom area of the back sheet when removing the aluminum frame from the solar cell module (see fig. 2).
The thickness of the ceramic support (A) is not particularly limited, but is preferably about 10 to 60 mm.
As the ceramic support body (a) described above, a product called a ceramic foam, a ceramic filter, or a ceramic foam filter made of alumina, silicon carbide, or cordierite is preferable.
When the method of the present invention is used for treating a waste solar cell, the solar cell module is stacked on the ceramic support (a) such that the back sheet surface thereof is located on the lower side. When the back plate surface is positioned on the lower side, the resin components constituting the back plate and the sealing resin layer are melted by heating and then flow out in the direction of the ceramic support body (a) due to the action of gravity.
Since the ceramic support (a) is porous, the contact area between the resin flowing down and the atmosphere in the pyrolysis furnace increases. Therefore, the combustion efficiency by further heating is improved, and the occurrence of "soot" can be suppressed.
< porous Material (B) >
In the porous material (B) supporting a transition metal oxide used in the present invention, the transition metal oxide has the ability to adsorb oxygen in an oxidized state and decompose an organic compound having an aromatic ring generated by oxidative decomposition in the combustion of an aromatic resin. For example, chromium (III) oxide is in a reduced state at room temperature and in emerald green color, but if it is heated to 400 ℃ or higher in the presence of oxygen, oxygen is adsorbed and changes color to dark green in an oxidized state.
The present inventors have found that when chromium oxide (III) is coated on a ceramic support similar to the ceramic support (a) (e.g., a ceramic filter) and disposed in a furnace, almost no "soot" adhering to the ceramic filter is generated. It is considered that this is because the organic compound having an aromatic ring is decomposed by the transition metal oxide, thereby suppressing the occurrence of "soot". This phenomenon is known to occur also in iron (III) oxide, copper (II) oxide, titanium (IV) oxide, and the like.
In view of the above, when at least a part of the resin constituting the back sheet is an aromatic resin such as PET (a resin having an aromatic group as a part of the repeating unit), it is preferable to previously allow the transition metal oxide to be present in the furnace from the viewpoint of suppressing the generation of "soot".
As the aforementioned transition metal oxide, for example, oxides of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury may be used without any limitation.
Among them, preferred are: oxides of a first transition element of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, oxides of a second transition element of yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, oxides of a third transition element of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, and more preferably transition metal oxides such as titanium (IV) oxide, chromium (III) oxide, iron (III) oxide, and copper (II) oxide of rutile type or anatase type can be suitably used. They may be in the state of a composite oxide.
In order to increase the contact area, the transition metal oxide is preferably supported on the porous material (B) and is present in the furnace in advance. The porous material (B) may be the same material as the ceramic support (a) as long as it is stable at the combustion temperature of the resin component. The shape of the porous material (B) is not particularly limited as long as it can be used as a so-called catalyst support, but is more preferably a plate-like porous molded body similar to the ceramic support (a) on which the solar cell module is placed.
As for the method of supporting the aforementioned transition metal oxide on the porous material, a known technique can be used without any limitation. Specifically, a method of impregnating and supporting a solution containing a transition metal oxide into a porous material using dip coating, wash coating, spray coating, spin coating, or the like is generally used. Thereafter, the method of removing the solution by heating to the boiling point or more of the solution is simplest. Further, a thermal spraying technique of spraying a substance obtained by melting a transition metal oxide onto a porous material may be used.
In the present invention, a ceramic support (A) on which a solar cell module is placed on a porous material (B) on which the transition metal oxide is supported.
The porous material (B) supporting a transition metal oxide is preferably not in direct contact with the solar cell module, and more preferably is disposed below the solar cell module without being in direct contact therewith. This is because contamination of the porous material (B) by nonflammable components such as fillers contained in the back sheet of the solar cell module and the like is less likely to occur, and when the porous material (B) supporting the transition metal oxide is repeatedly used, there is no need to perform a regeneration treatment or the like.
The size of the porous material (B) is preferably equal to or larger than the bottom area of the ceramic support (a) in terms of stability of the object to be treated including the solar cell module. The thickness of the porous material (B) is preferably about 10 to 60 mm.
Examples
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
[ example 1]
Using the pyrolysis furnace 20 shown in fig. 3, the object to be treated 23 including the solar cell module 7 is moved by the chain conveyor 24 from the left side (inlet side) to the right side (outlet side) of the pyrolysis furnace section 22 in the furnace, thereby performing heat treatment.
As the solar cell module 7, an experiment was carried out using "REC solar panel" manufactured by REC (cell type: REC PE polycrystalline solar cell, size: 1665 mm. Times.991 mm. Times.38 mm). The aluminum frame 10, junction box and connector were removed before the heat treatment using a spatula and a hammer in such a manner as not to damage the glass.
As the ceramic filter of the ceramic support (A) 2, 10ppi 400mm. Times.300 mm. Times.30 mmt (porosity: 87.8%) of Senday spring filter FCF-2 (made of silicon carbide) was used.
While suspending light-mixing grade-1 chromium (III) oxide (fuji film and wako pure chemical industries, ltd.) in water, the above ceramic filter was immersed and dip-coated, and dried at 450 ℃. The mass before coating was 1480g, and the mass after coating and drying was 1790g.
A2100 mm × 1210mm × 50mm iron tray with a grid was prepared, 21 ceramic filters coated with chromium oxide were used, and a 2100mm × 1200mm × 30mmt porous material (B) 1 was provided in the lowermost stage. A2100 mm X1200 mm X30 mmt ceramic support (A) 2 was provided on the middle stage of the ceramic filter using 21 pieces of 400mm X300 mm X30 mmt ceramic filter. The solar cell module 7 is further provided thereon such that the back sheet 3 is positioned on the lower side.
The thermal decomposition furnace 20 is used as a gas furnace. As the gas furnace, a hot air circulation type heat treatment apparatus of a takt conveyor chain blowing type having a furnace length of 5400mm, a furnace width of 2300mm and a furnace height of 280mm was used. A metal burner MJPEG-200K is used as the gas nozzle portion 21, and a mixed gas of liquefied petroleum gas and air is introducedAnd burned to thereby perform heating. The foot-standing machine is used for manufacturing a 6.0-LF limit load fan (450 m) 3 2.0kpa, 30kw) from the lower side of the thermal decomposition furnace section 22, the heated mixed gas was supplied through the slit extrusion, and blown vigorously against the porous material (B) 1 to enable heat exchange, and a part of the circulated heated gas was discharged.
The object 23 to be treated, which was prepared as described above and includes the solar cell module 7, the ceramic support (a) 2, and the porous material (B) 1, was held for 6.5 minutes in each of 3 zones in the furnace from the inlet side toward the outlet side of the pyrolysis furnace section 22, transferred with a tact, and subjected to a heating treatment for a total of 19.5 minutes in the pyrolysis furnace 20. The inlet side is a temperature increasing portion 27, and the region where the resin component contained in the solar cell module 7 burns is a burning portion 28. A thermocouple thermometer was attached to the center of the upper portion of the middle ceramic support (a) 2, and the temperature of the object to be treated 23 was measured.
In the heating treatment, the oxygen concentration measuring unit 26 adjusts the ratio of air in the supplied mixed gas so that the oxygen concentration of the combustion unit 28 is in the range of 6vol% or more and less than 15vol%, and the heating temperature and the supply amount of the supplied mixed gas are adjusted so that the temperature of the object to be treated 23 in the combustion unit 28 is 470 ℃ or more.
As a result of the heat treatment as described above, as shown in fig. 4, the temperature in the furnace can be stably controlled to the range of 470 to 530 ℃. That is, it was found that stable temperature control and treatment of the object to be treated 23 can be achieved by slow combustion without flame in a low-oxygen atmosphere. After the heat treatment, the tempered glass 6 was successfully recovered without breaking, and the battery cell 5 and the inorganic powder were also successfully recovered. Furthermore, no adhesion of "soot" was observed on the ceramic filter used as the lowermost stage of the porous material (B) 1.
Comparative example 1
The heat treatment of the object 23 to be treated including the solar cell module 7 was performed in the same manner as in example 1, except that the oxygen concentration measuring unit 26 was used to set the oxygen concentration in the combustion unit 28 to 15vol% or more. As a result, as shown in fig. 4, since the temperature in the furnace rapidly rises due to the explosive combustion of the flame, countermeasures such as suppression of the supply amount of the supply gas are required. That is, it was found that it was difficult to stably control the furnace temperature under a normal oxygen atmosphere, and as a result, the treatment cost was increased.
Description of the reference numerals
1: porous material (B) supporting transition metal oxide
2: porous ceramic support (A)
3: back plate
4: resin layer for sealing (EVA)
5: battery unit
6: tempered glass
7: solar energy battery component (X)
8: decking or wire netting
9: gas stove or electric stove
10: aluminum frame
20: thermal decomposition furnace
21: gas nozzle
22: thermal decomposition furnace part
23: object to be treated
24: chain conveyor
25: temperature measuring part
26: oxygen concentration measuring part
27: temperature raising unit
28: combustion section
Claims (3)
1. A method for continuously treating waste solar cells, comprising: a solar cell module comprising a resin back sheet and a sealing resin layer is heated in a pyrolysis furnace to melt and oxidatively decompose a resin component contained in the solar cell module,
the heating step is performed as follows: moving the solar cell module in a furnace from an inlet to an outlet of the pyrolysis furnace in a state where the solar cell module is placed on a porous ceramic support (A) and the ceramic support (A) is placed on a porous material (B) supporting a transition metal oxide,
the thermal decomposition furnace includes a temperature raising section at a stage where the temperature of the solar cell module rises and a combustion section at a stage where the resin component is oxidatively decomposed, and the oxygen concentration in the combustion section is controlled to be in a range of 6vol% or more and less than 15 vol%.
2. The method for treating waste solar cells according to claim 1, wherein a plurality of the solar cell modules in the heated state exist in the thermal decomposition furnace.
3. The method for treating a waste solar cell according to claim 1 or 2, wherein valuable substances remaining on the ceramic support (a) are recovered after the heating step.
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| JP2020-114353 | 2020-07-01 | ||
| PCT/JP2021/024728 WO2022004781A1 (en) | 2020-07-01 | 2021-06-30 | Waste solar cell processing method |
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| CN115769384A true CN115769384A (en) | 2023-03-07 |
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| JP (1) | JPWO2022004781A1 (en) |
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| DE19731160C2 (en) | 1997-07-21 | 1999-05-27 | Pilkington Solar Int Gmbh | Process for separating the components of a laminated glass pane |
| JP4602872B2 (en) | 2005-08-26 | 2010-12-22 | 昭和シェル石油株式会社 | CIS-based thin film solar cell module component recovery method |
| JP2011080664A (en) * | 2009-10-06 | 2011-04-21 | Takusen Ito | Method and device for thermal-decomposing, carbonizing, and gasifying waste |
| JP6297254B2 (en) | 2012-11-30 | 2018-03-20 | 株式会社新菱 | Method for collecting solar cell element constituent materials |
| JP6596732B2 (en) * | 2015-03-31 | 2019-10-30 | 株式会社ジンテク | Method for recovering valuable material from solar cell panel and processing device for recovery |
| WO2020031661A1 (en) | 2018-08-06 | 2020-02-13 | 株式会社トクヤマ | Method for recovering valuable object from solar cell module |
| JP2020142218A (en) * | 2019-03-08 | 2020-09-10 | 株式会社綿谷製作所 | Disassembling apparatus of solar cell panel, and disassembling method of solar cell panel |
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- 2021-06-30 KR KR1020227044450A patent/KR20230031216A/en active Search and Examination
- 2021-06-30 AU AU2021300100A patent/AU2021300100A1/en active Pending
- 2021-06-30 US US18/013,077 patent/US20230241655A1/en active Pending
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| Publication number | Publication date |
|---|---|
| KR20230031216A (en) | 2023-03-07 |
| EP4176984A1 (en) | 2023-05-10 |
| AU2021300100A1 (en) | 2023-02-02 |
| US20230241655A1 (en) | 2023-08-03 |
| JPWO2022004781A1 (en) | 2022-01-06 |
| WO2022004781A1 (en) | 2022-01-06 |
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